Wood pulping-delignification in the presence of high sulfur dioxide concentrations



Aug. 4, 1970 L. E. HERDLE E L 3,

WOOD PULPING-DELIGNIFICATION IN THE PRESENCE OF HIGH SULFUR DIOXIDE CONCENTRATIONS Filed Oct. 16, 1967 2 Sheets-Sheet 1 COMB/NED A a /35 c- C kggffl PULP/N6 I a I Q /00 cy I \Q\ I I I l I l l l l L L l I TIME, HOURS FIG. 2

. AND PUL P/IVG l l l l l 2 3 4 5 TIME, HOURS FIG. 3

V k LLOYD 5. HERDLE ALEXANDER WALKER, m.

FRANK L ELLS /0- R5 Y l l I l I I I l /0 20 40 60 .90 s0 V w A TTORNEYS" Aug. 4, 1970 E, HERDLE ET AL 3,523,060

W002) PULPING-DELIGNIFICATION IN THE PRESENCE OF HIGH SULFUR DIOXIDE CONCENTRATIONS Fil :d. Oct. 16, 1967 2 Sheets-Sheet 2 30% 70 Q: KAPPA N0. 60 xx- YIELD 3 Q a 30 I 20 3 IOP- I l l 1 l //5 125 I TEMPERATURE "a o- KAPPA N0.

x- --x Y/ELD Y/ELO(%/ AND KAPPA NUMBER 5 6 l l I I l l 1 0 0.5 /.0 [5 a 2.0 2.5 L 3.0

TIME (HOURS/AT /40 C LLOYD 6'. HERDLE ALEXANDER WALKER,JR

B AAAP% ATTORNEYS United States Patent 3,523,060 WOOD PULPING-DELIGNIFICATION IN THE PRESENCE OF HIGH SULFUR DIOXIDE CONCENTRATIONS Lloyd E. Herdle, Alexander Walker, Jr., and Frank L. Wells, Rochester, N.Y., assignors to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey Filed Oct. 16, 1967, Ser. No. 675,607 Int. Cl. D21c 3/20 U.S. Cl. 16276 17 Claims ABSTRACT OF THE DISCLOSURE This invention relates to acid sulfite processes for delignifying and pulping Wood. More particularly, the present invention is directed to processes involving the delignification and pulping of wood in the presence of sulfur dioxide concentrations of from 30 to about 80 weight percent of sulfur dioxide and at temperatures within the range of from about 120 C. to about 145 C.

BACKGROUND Conventional acid sulfite pulping processes, in which wood is converted into a form in which it can be used directly for the manufacture of paper, cellulose esters, and the like, involve initially a fairly long (3-4 hours, at least) delignification step wherein the Wood is treated with a few percent (68%, based on the weight of the aqueous portion) of S0 dissolved in water. A small amount of material containing alkali metal or alkaline earth metal cations is always used in contemporary commercial sulfite pulping processes along with the S0 During this delignification step the temperature of the cook is usually gradually increased (over a period of at least 3-4 hours), from below about 100 C. to about 120 C. (the minimum temperature necessary to obtain the desired degree of pulping in such systems). Pulping temperatures in conventional sulfite pulping processes are generally Within the range of from about 120 C. to about 145 C.

During the time the temperature of the cook is being gradually raised, most of the lignin in the wood is gradually reacting with the dissolved sulfite to yield a lignosulfonate type material that is soluble in the liquor. Thus, the greatest portion of the lignin that was originally in the wood is removed in the form of lignosulfonates dissolved in the sulfite liquor that is ultimately drained away from the pulp product. Removal of almost all of the lignin in this manner is essential for the manufacture of useful, bleachable sulfite pulp.

Such conventional delignification processes have been worked out through many years of experience. Although it is desireable to use a very fast, higher temperature delignification step (rather than such a prolonged pro cedure), it was heretofore necessary to use such a gradual increase in reaction temperature to make a soluble lignosulfonate. Otherwise (by raising the temperature of such conventional sulfite cooks swiftly to the pulping range; i.e. substantially less than 3 hours), a discolored, so-called burned pulp resulted. Such a burned pulp could not be bleached readily, and was believed caused by resinification of the lignin, resulting in insoluble lignin derivatives that could not be removed from the wood. This necessity to delignify Wood chips initially at temperatures below about 110 C. (before raising the cook temperature to the pulping range of 120 C. or more), particularly in the absence of large amounts of combined S0 in the cook, is described in detail at pages l58l62 of volume 1 of Pulp and Paper, edited by James P. Casey (Interscience Publishers, 1960), and on 3,523,060 Patented Aug. 4, 1970 pages 267 and 272 of TAPPI, volume 37, No. 6 (June 1954), in an article by G. A. Richter and L. H. Pancoast, Jr. entitled Sulphonation of Wood Lignin.

Methods of improving the quality of sulfite pulps and/ or substantially decreasing the amount of processing time required to make a final, bleachable pulp are being continuously sought by those in the Wood pulping art as significant means for reducing the cost of manufacturing such useful materials. In addition, methods for manufacturing sulfite pulp having sufficiently high quality to be useful directly (after being bleached, but Without the need for any additional refinement) as a raw material for the manufacture of high quality esterified cellulose such as cellulose acetate, cellulose propionate, cellulose phthalate and the like suitable for use as photographic film base, for example, have been actively sought for many years.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a graph of temperature versus time in a conventional process of delignifying pulp with 8% total S0 content;

FIG. 2 is a graph of temperature versus time in the process of the present invention of delignifying pulp with 40% total S0 content;

FIG. 3 is a graph of the effect of various amounts of S0 on the Kappa Number of pulp in the present invention;

FIG. 4 is a graph of percent yield and Kappa Number versus temperature in the process of the present invention of delignifying pulp with 30% total S0 content; and

FIG. 5 is a graph of percent yield and Kappa Number versus time at a constant temperature in the present invention.

THE PRESENT INVENTION It has now been discovered that both improved quality and substantially reduced processing times can be obtained in sulfite pulping processes (a) by utilizing very large quantities of sulfur dioxide, at least during the de lignification step of the processes, and (b) by forcing the delignification step at high temperatures that were heretofore believed to be impracticable, because of the above-described burning problem. Evidently, for some surprising reason that is presently not known, the use of the very high levels of S0 (i.e., at least about 30%) overcomes the burning problem. One of the very valuable results of practicing the present invention can be illustrated by the fact that, whereas heretofore, it was believed necessary to consume at least about 7-8 hours to manufacture acceptable, bleachable sulfite pulps (having Kappa Numbers below about 30), the present invention makes it possible to manufacture similarly acceptable pulps in substantially less than half that time.

The most important elements that contribute to the success of the present invention are (1) the use of at least about 30% of S0 and (2) the quick attainment of pulping temperatures. Whereas pulps having acceptable Kappa Numbers (i.e., below about 40) were not obtainable via conventional procedures within total processing times of less than about 6-10 hours, it is possible in the practice of this invention to attain this goal in 2 /2 hours, or even less time. In the present processes, generally from about 30 to about weight percent of 80 (based on the combined weight of the water and the S0 in the cook) should be present in the delignification reaction mass (containing the particulated wood, water, S0 and any other desired adjuvants), when the temperature of the cook is raised above about C. Note that in this context the reaction mass is not termed a cook unless some S0 is present therein. However, the

use of from about 30% to about 50% of S is preferred because of the necessity for stronger autoclaves when relatively higher levels of S0 are used. The effect of various amounts of $0 on the Kappa Number of spruce pulp that was prepared by a procedure such as that described in Example 1, below is illustrated in FIG. 3 of the drawings.

As it was pointed out above, it is also essential in the practice of this invention, to push the temperature of the cook into the pulping range, i.e., from about 120 C. to about 145 C. quickly, i.e., in at most about 2 hours, and preferably in less than about 30 minutes of the time the necessary high level of S0 is attained in the cook. This is in direct contrast to what has heretofore been possible, because initially, at least several hours reaction time below pulping temperatures were necessary to avoid insolubilization of the lignin. A typical prior art process is graphically compared with one of the present processes in FIGS. 1 and 2. The valuable time-saving advantage that can result from practicing the present invention can readily be appreciated from a comparison of FIGS. 1 and 2. Note that, in the conventional processes of FIG. 1, if the temperature of the cook is pushed into the pulping range before all of the lignin has been solubilized (i.e., in less than 34 hours), the pulp is burned, thereby practically destroying its usefulness. By comparison, in the process illustrated by FIG. 2, with 40% S0 present in the cook, forcing the temperature of the cook to 135 C. in less than 15 minutes surprisingly resulted in no burning Whatever. As a matter of fact, reaching pulping temperatures over prolonged periods of time (as in conventional processes) are actually somewhat detrimental to the pulps when the very high S0 levels of this invention are used. In addition, prolonged exposure (i.e. longer than about 5 hours) at pulping temperatures is also detrimental to the Kappa Numbers of pulp manufactured via the present processes. Since relatively higher pul ing temperatures make it necessary to terminate the pulping process even sooner than this (for example, for best results, pulping at 140 C. should be terminated after at most about 2 hours as illustrated by FIG. 5), it can be seen that the actual preferred pulping times of the present processes will vary somewhat, depending upon the actual temperature profile utilized; generally higher temperatures require relatively shorter reaction times.

The particular manipulative procedures and the particular equipment that are utilized in the practice of this invention are not critical insofar as the successful practice thereof is concerned. All that is necessary is that, at least during the initial minutes of time in which the cooks of the present invention are exposed to pulping temperatures, enough pressure is maintained on the reaction mass to keep the level of S0 above the minimum useful level. Thus, in perhaps the simplest embodiment of the present processes, while liquid S0 water, and wood chips can simply be blended at about room temperature in an autoclave and the resulting cook is then heated quickly to pulping temperatures and held at this point for the time necessary to produce the desired bleachable pulp, still another embodiment involves the charging of the autoclave with wood chips followed by the introduction of hot (already at pulping temperatures) acidic aqueous concentrated S0 solution. This latter technique represents a method for obtaining the shortest reaction times, and also represents a preferred embodiment of the present processes. Still another technique for accomplishing the present processes involves the initial charging of very concentrated S0 solution onto the wood cellulose followed by a relatively short exposure (i.e., at most about one hour) of the resulting concentrated S0 cook to pu ping temperatures after the required initial quick attainment of a pulping temperature. Then, before the completion of pulping, the level of S0 can be reduced to as low as 56%, if desired.

By this latter procedure, the actual time the pulping step is terminated becomes less important.

In the following examples, all parts are by weight unless otherwise specified.

Example 1 Into a conventional glass lined autoclave able to withstand internal pressures of at least 600 pounds per square inch are charged 50,000 parts of Eastern spruce chips and 420,000 parts of water, followed by 180,000 parts of liquid S0 The liquid S0 is suspended in a plastic container over the aqueous suspension of chips until the autoclave is sealed. Then the plastic container is breached and the S0 permitted to blend with the wood chips and the water. superheated steam is immediately applied to the jacket of the autoclave, the cook thereby being heated to B5 C. in about 15 minutes. Thereafter, over the next 2 hours, the temperature of the cook is maintained within about 1 degree of C. At the end of this time, the S0 is vented from the autoclave, and the resulting cook is filtered. The pulp is then washed several times with water, dried, and analyzed. Data from the analysis appears in Table 1, below.

TABLE 1 Yield (percent) 32 Kappa No. 20 Screenings (percent) 1O *Lignin (percent) 5 Pentosans 0.3

Other woods can be treated in this same manner with correspondingly excellent results.

Another surprising benefit that can be obtained from practicing this invention can be appreciated from an understanding of the foregoing example. Thus, it is especially noteworthy that the present prcoesses can be practiced in the absence of so-called combined S0 that is, 50 that has been chemically combined with an alkali metal or alkaline earth metal base such as NaOH, MgCO Ca(OH) and the like. Since no combined S0 is needed in the practice of the present processes, one of the diflicult waste disposal problems that presently vex sulfite pulp manufacturers can simply be avoided. It can be appreciated that this is a very significant contribution to the art, since waste disposal is one of the greatest problems facing contemporary pulp manufacturers. It should be noted, however, that the present processes can nevertheless also be successfully practiced in the presence of combined S0 if manufacturers prefer to use combined. Combined S0 (for example, in the form of bisulfite) results When a basic material is added to an acidic sulfite cook. For example, the addition of calcium hydroxide to the cook results in the formation of calcium bisulfite in the presence of excess S0 Still another advantage of the present processes is that they are useful in combination with certain improved processes such as that described in U.S. Pat. 2,060,068. Note that in this patent the use of lower aliphatic alcohols such as isopropanol, ethanol, methanol, butanol and pentanol (that are miscible with acidic sulfite cooks), in conjunction with the usual materials in sulufite pulping cooks are described. Lower aliphatic carboxylic acids (such as acetic, formic, propionic, butanoic and pentanoic acids) and ethylene glycol and propylene glycol can also be used in the present processes. Thus, while the abovedescribed very valuable benefits can be obtained by practicing the present processes in the absence of either lower aliphatic alcohols, ethylene glycol, butylene glycol, and/ or lower aliphatic acids, still more valuable, significantly improved results can be obtained by utilizing one or more of these organic adjuvants in the present processes. Accordingly, the use of lower aliphatic alcohols miscible aliphatic glycols, and/ or lower aliphatic acids in the present generic processes constitute preferred embodiments of this invention.

While small amounts of such miscible organic adjuvants will result in at least some improvements, generally, when lower aliphatic alcohols are utilized in these processes, amounts within the range of from about to about 50, and preferably from about 5 to about 30, weight percent (based on the combined weights of the liquids in the cook) should be utilized. Similarly, when lower fatty acids are used in these processes, generally noticeably im roved results can be obtained when from about 5 to about 50, and preferably from about to about 30 weight percent (based on the combined weights of the liquids in the cook) should be utilized. The miscible glycols should be treated as the lower aliphatic alcohols, insofar as the quantities in which they are useful is concerned. When two or more of the group consisting of these alcohols, glycols, and fatty acids are used in the same cook, somewhat lower amounts of each yield excellent results. The following examples illustrate some of the additional benefits that can be obtained by using this particular preferred embodiment.

Examples 2-8 These examples are carried out in the same manner as that described in Example 1, above, except that, where lower fatty acid, glycol, or alcohol are utilized, the initial amounts of water used is reduced accordingly. Data for Example 1 is repeated in Table 2 for convenience.

processes. In this example, the processes of Examples 917 are followed, using Douglas-fir chips, and a pulping temperature of 135 C. In Table 4, below, the total processing time" includes a -minute heatup to 135 C. and subsequent pulping at 135 C. The liquid charge contains 30% S0 55% water, and 15% isopropyl alcohol.

TABLE 4 Total Processing Time, hours 1. 25 1. 75 2. 25 2. 75 3. 25 Pressure, p.s.i. 380 385 400 395 410 Yield, percent... 36. 7 31. 5 33. 4 25. 6 28. 0 Screenings, percent 13. 3 4. 5 3. 6 3. 1 2.8 Kappa No 24. 0 19. 2 l8. 6 30. 5 37. 4: Lignin, percent 8 Pentosans, percent 1. 8 1. 5 0. 9 0. 6 0. 6

Example TABLE 2 Ex.1 Ex.2 Ex.3 1311.4 Ex.5 Ex.6 Ex.7 Ex.8

Liquid charged:

S02, percent 30 30 30 30 30 30 30 30 1120, percent 70 55 55 55 55 55 55 45 011300011, percent 15 15 15 15 (01192011011, pereent 15 15 15 10 Pressure, p.s.i 505 390 395 400 400 400 428 410 Analyses:

Yield, percent 32 36 37 31 25 31 29 Screenings, percent 11 4. 5 1. 1 23. 2 7. 1 21. 2 8. 9 1. 5 Kappa No 20 11 6 22 10 26 15 Lignin, percen 5 2 3 6 4 4 Pentosans, pereent 0. 3 1. 2 1 1 1 0. 6 0. 6 0. 5

1 Eastern Spruce. 2 Southern pine. 3 Douglas-fir.

Examples 9-18 TABLE 5 In the following examples, data for which are sum- S0 (percent) 36 marized in Table 3, manipulative procedures are prac- H O (percent) i s 59 tically identical to those in Examples 1-8, except that the Isopropanol (percent) 5 pulping temperature is 140 C. in Examples 918 and the Pressure during cook, p.s.i 445 total time during which the cook is held at pulping tern- Yield (percent) 32.1 perature is only one-half hour. Thus, 1I1 Examples 9-18, Screenings (percent) 10.0 the total processing time, including both delignification Kappa No. 6.3 and pulping of the wood chips is only one hour. Pentosans (percent) 1.3

TABLE 3 Ex. 9 Ex. 10 Ex. 11 Ex. 12 Ex. 13 Ex. 14 Ex. 15 Ex. 16 Ex. 17 Ex. 18

Liquid charged:

S02, percent 30 30 30 30 30 30 30 30 30 30 1120, percent 70 55 55 55 70 55 55 55 CILOOOH, percent 15 15 15 (CH3)2CHOH,1)8l"CDlJ. 15 15 15 Ethylene glycol, percent 15 Pressure, p.s.l 490 400 385 485 385 385 490 395 400 455 Analyses:

Yield, percent 30. 0 35. 2 32.5 40. 3 32. 6 43. 6 31. 5 34. 7 33. 3 32. 2 Screenings, percent" 3. 1 0.5 0. 1 1. 5 0.5 0. 9 30.6 15. 6 10. 8 1. 2 Kappa No 14. 4 5. 3 6.0 14. 5 7. 7 9.1 19. 2 15.8 14. 8 s. 0 Lignin, percent 3. 4 l. 2 1. 2 2. 6 1. 2 1. 5 3. 7 3. 0 2.8 Pentosans, percent 0.8 1. 7 2. 2 4. 9 1. 2 6. 3 2. 9 4. 1 4. 3 0. 7

l Gumwood. 2 White Birch. 3 Alder. 4 Eastern Spruce.

Example 19 Examples 21-25 An additional advantage of practicing the processes of the present invention is that Douglas-fir can be converted to an acceptable, bleachable sulfite pulp thereby.

Cooks were conducted as in Example 20, except that the hot liquid blend is adjusted to contain varying amounts of isopropanol. Analyses of the pulps resulting from these This is not possible via conventional acidic sulfite pulping cooks are summarized in Table 6.

lation grade pulps via the sulfite process without the necessity for such costly refinement step.

Another specific embodiment of the present processes involves the maintenance of at least about 30 weight percent of S in the cook during only the first portion of TABLE 6 the present pulping step. Thus, after at least about minutes of exposure to pulping temperatures, (preferably 21 EX'22 Ex'zs ELM EX'25 after at least about 15 minutes within this temperature 8 2. percent 36 36 36 36 36 range) some of the S0 can be vented from the reactor if ifghgi gzgzggijj i3 i2 23 i3 is 5 desired. Apparently the most critical stage of the present Yie1d. perce11t 2-5 g 2-2 processes is the initial step involving the quick heating ggg ligfiii f fjjj 232 5 1 :9 of the wood in presence of at least about 30% solutions Pentosans, percent 1.6 0.7 2.0 1.9 1.9 f SO2 Pressure 400 435 355 335 280 The invention has been described in detail with particu- 10 lar reference to preferred embodiments thereof, but it Examples 2640 will be understood that variations and modifications can The following examples illustrate Still another very be effected within the spirit and scope of the invention valuable benefit that can be Obtained by practicing the as described hereinabove and as defined in the appended present invention. Thus, via the present processes, bleachclalmsable sulfite pulps can be obtained that are useful directly We 61mm: as raw materials for high quality cellulose esterification In a P P fOf ufa turing bleachable wood processes (without the necessity for any additional re- P p from P Q F W Od WhlCh process comprises the finemen treatments such as those that must be used on Steps f Q g Sald Wood y Converting K105i conventional sulfite pulps in order to adapt them for such of f hgnfn P 5 W to q f 1 1gnS111f9I}a1eS y esterification processes) reacting said lignm with sulfur dioxide in an acidic aque- Table 7, below, summarizes data resulting f meat. ous slurry of said wood at temperatures below about 120 ing several samples of wood chips in the following and subseqllfintly compkitmg the P p g 0f the manner; sulting treated wood at a temperature between about 120 1 pelignificazion d l Th Processes of E C. and about 14 5 O the improvement which comprises ample 1, above, are followed, varying only the amount dellgnifymg Bald Wood y forming an acidic. of water (when the lower aliphatic carboxylic acid or the aqueous Suspension y iHtBrmiXing Said WOOd With lo aliphatic lcohol i d) t keep co tant th t tal water and at least weight percent of sulfur dioxide, amount of liquid in the autoclave. Total processing based on the combined weight of said water and said time includes both the warmup and the pulping steps. a sulfur dioxide, and (2) raising the temperature of (2) Bleaching.The unbleached pulps are bleached in 00 said acidic aqueous suspension quickly as compared a conventional manner by sequentially washing them with with prior art processes, within a period of at most first an alkaline aqueous solution of chlorine dioxide and 2 hours, to at least 120 C., and then a dilute aqueous solution of HCl. (b) thereafter, until said wood is pulped, maintaining (3) Esterificati0rz.-A conventional esterification procthe temperature of said acidic aqueous suspension ess is followed, whereby the bleached pulp is treated as 39 between about 120 C. and about 145 C. and simuldescribed in an article by L. E. Herdle, L. H. Pancoast, taneously maintaining a concentration of at least 30 In, and R. H. MacClaren in TAPPI, vol. 47, pages weight percent of sulfur dioxide insaid acidic aqueous 617-620 (October 1964). A description of the clarity suspension with the aid of sutlicient pressure for at and color" tests is also contained in this Herdle et a1. 40 least 15 minutes after the temperature of said acidic publication. Samples yielding acetate solution color aqueous suspension has reached 120 C. values below about 300 and clarity values of 10 or 2. An improved process as in claim 1, wherein said more are considered acceptable acetylation grade" pulps. concentration of said sulfur dioxide in said acidic aqueous TABLE 7 Ex.26 1321.27 Ex. 28 Ex.29 Ex. 30

Pulping data:

S02, percent 30 30 30 30 30 1-120, percent 6O 55 55 0131300011, percent... 10 15 (CHmGHOH, percent 10 15 Total process time, hrs 2. 0 2. 0 2. 5 2. 5 2. 5 Yield, percent 34. 0 35. 0 33. 0 26. 2 24. 9 Pressure, p.s.i 405 435 4.95 415 425 Acetate solution data:

Clarity 10 11 14 1e 15 Color 185 275 185 1 Eastern spmce.

2 Gumwood.

The acetate solution data for a bleached sulfite pulp suspension is between 30 and about 80 weight percent, that has not been further refined, by comparison reveals 60 based on the total Weight of liquids in said acidic aqueous that such materials are completely unacceptable for use suspension in the manufacture of 10W hale, high y, colorless 3. An improved process as in claim 2, wherein said 6611111056 acetate film bases- Hefetofoffl, W it was f temperature is raised quickly until it is within the range sired to use sulfite pulps as raw materials for making of from about C to abmlt C. snot} hlgh quahty caglulose ff e to first 60 4. An improved process as in claim 2, wherein said sPblected to a costly refinemen? i mvolvmg the acidic aqueous suspension also contains at least 5 wei ht tional treatment of the pulp with culute aqueous NaOH solution. Such additional refinemen often caused losses percent of i imsmble orgamgadjuyant Selected from h of yield amounting to as much as 30% i The present group consisting of lower aliphatic alcohols, lower alivention makes it possible to manufacture so-calledacety- 70 Phanc carboxyhc aclds athylene glycol, and butylene glycol.

5. An improved process as in claim 4, wherein said miscible organic adjuvant is a lower aliphatic alcohol; the amount of said alcohol in said acidic aqueous suspension being from about 5 to about 30 weight percent,

based upon the total weight of liquids in said acidic aqueous suspension.

6. An improved process as in claim 4, wherein said miscible organic adjuvant is a lower aliphatic carboxylic acid, the amount of said carboxylic acid being from about 10 to about 30 weight percent, based upon the total weight of liquids in said acidic aqueous suspension.

7. An improved process as in claim 4, wherein said miscible organic adjuvant is a glycol selected from the group consisting of ethylene glycol and propylene glycol.

8. An improved process as in claim 5, wherein said alcohol is isopropyl alcohol.

9. An improved process as in claim 5, alcohol is ethyl alcohol.

10. An improved process as in claim 5, alcohol is amyl alcohol.

11. An improved process as in claim 6, carboxylic acid is acetic acid.

12. An improved process as in claim 6, carboxylic acid is butyric acid.

13. An improved process as in claim 6, carboxylic acid is propionic acid.

14. A process which comprises (1) blending wood chips with a hot mixture which consists essentially of water and from 30 to about 80 weight percent of sulfur dioxide, the temperature of said hot mixture being within the range of from about 120 C. to about l45 C. during said blend ing; and (2) maintaining the temperature of the resulting blend within said range for at least 30 minutes until said wood chips are pulped; a concentration of at least 30 weight percent of said sulfur dioxide being maintained wherein said wherein said wherein said wherein said wherein said in said resulting blend with the aid of suflicient pressure for at least 15 minutes.

15. A process as in claim 14, wherein said hot mixture contains, in addition to said water and said sulfur dioxide, from about 5 to about 30 weight percent, based on the total weight of liquids in said hot mixture, of a lower aliphatic alcohol.

16. A process as in claim 5, wherein said lower aliphatic alcohol is replaced with a glycol selected from the group consisting of ethylene'glycol and propylene glycol.

17. A process as in claim 14, wherein said hot mixture contains, in addition to said water and said sulfur dioxide, from about 10 to about 30 weight percent, based on the total weight of liquids in said hot mixture, of a lower aliphatic acid.

References Cited UNITED STATES PATENTS 11/1936 Groombridge et a1. 16277 10/1965 Madison 16284 X US. 01. x11. 162 -77, s3, s4

mg UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent 3.523.060 Dated 8/4/70 Inventor(s) Lloyd E. Herdle, Alexander Walker, Jr. and Frank L.

Wells, Rochester, N.Y. It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

In column 6, line 24 delete "l355 C" and substitute therefor ---l35C--.

In Table 3, line 11, delete "32,2" and substitute therefor 32o3 o In Table 3, line 12, delete "0 5" and substitut therefor ---0. 6--. This is in column 5 of this table).

mm m: sum

Altesfingoffiocr m1 mum, JR.

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